Gilsonite products



Patented Feb. 16, 19 26. v UNITED STATES PATENT OFFICE.

CHARLES N. ronans'r, or RAHWAY, NEW JERSEY, AssIGNon TO THE BARBER as;PHALT COMPANY, OEPHILADELPHIA, PENNSYLVANIA, A CORPORATION or was:

VIRGINIA.

.GILSONITE PRODUCTS.

No Drawing. Continuation of application Serial No. 318,536, 'filedAugust-19,1919. This application; filed September 19, 1922. Serial No.589,269. v

To all whom it may concern: York Testing Laboratory, and previously i Beit known that I, CHARLES N. FORREST, a principal assistant chemist inthe U. S. De-; citizen of the United States, and a resident partment ofAgriculture and inspector of asof Rahway, in the county of Union andState phalt and cement of the District of Columof New Jersey, have.invented certain new bia), published in 1905 by John Wiley &

and useful Improvements in Gilsonite Prod- Sons, llew York. NVhilecomparison of ucts, whereof the following is a specification. Days paperWith Richardsons summary 1 My invention relates to gilsonite products(especially pp. 202-203) shows that many of and their manufacture, andits object is the Days results and inferences were not cred- 10production from gilsonite of various useful ited, the two accounts doagree entirely in resubstances in a commercially practicable and gardingthe possibility of useful products economical way. The novelty of myinvenfrom gilso'nite as a pure matter of speculation resides not only inmy processes and tion. methods of manufacture, but extends, also to Days work avowedlyfailed of attaining some of the substances obtained,which are in the definite information that he sought rethemselves new.garding the nature of gilsonite; and his own 7 Q As to certain divisiblecommon subject tentative conclusions go very little further matter, mypresent application is a continuthan that distillation of gilsonite isunprom .ation of my application, Serial No. 318,536, ising, and thatfuture work on the substance 30 filed August 19, 1919, which was itself,likeshould be along the lines of direct treatment wise, in part acontinuation of my applicawith reagents such as nitric and sulphuriction, Serial No. 195,721, filed October 10, acids accordingto amethodoutlined as a 1917 under the title Liquid hydrocarbon. result of hisinvestigation. \Vhile the in- Gilsonite is a natural solid bitumen, ofdefiniteness of his descriptions makes any at- 25 well known physicalproperties,including a tempt to repeat or reproduce his work quitepeculiar, characteristic concoidal fracture, futile, such data andresults as he does re- 30 found principally in certain sections of Utah.port, nevertheless, show very clearly that he As compared with othernatural bitumens in could not really have been working with true theirnative state, it is remarkable for its gilsonite at all,except, perhaps,in admix- 30 "cry high degree of purity. Its specific ture with dominantamounts of other subgravity at 7 7 F. varies over a range of, apstances.Thus he states that the material on proximately, 1.040 to 1.056. It hasbeen which he worked was lighter than water, used as an ingredient inpaints and var- Whereas in fact gilsonite is heavier; that nishes'; inpaving, waterproofing, and roofwhen heated, his materialgga-vea final,irre- 35 ing compounds; and in rubber manufacture. ducible residue ofsome 43%, whereas gil- Of the chemical nature or possibilities of soniteyields no more than 30% of residue; gilsonite, practically nothingfurther is that all the volatile matter driven off bydisknown.Scientific investigations heretofore. tillation was condensa'ble bywatereooling, attempted have been perfunctory, abortive ,whereasgilsonite yields such substantial pro.-

40 and inconclusive and, until my invention, portions as some 15% ofvapor not so conexploitation commercially has not even been densable,including some 13% of well known attempted. gases; that no solidseparated out in any of The confusion and vagueness of the worlds hisredistillations, whereas under the condiinformation regarding gilsoniteare well iltions of some of them he would have ob r lustrated by twopublished accounts: one in tained from. gilsonite a hard, crystallinewax,

a paper entitled Investigation of Utah gilhigher melting than paratiine;that his ma- 0 sonite. a variety of 'lasphalt, read June 18,- terialcontained but 0.32% of both oxygen 1895, bv IVilliam C. Day, ofSwarthmo-re and nitrogen together, whereas gilsonite con- College;before the Chemical Section of the tains about 2 to- 3% of nitrogenalone; and

50 Franklin Institute (published in its Journal that his refiningoperations consumed a pro- Vol. 140, pp. 221-237, September 1895) andportion of the oil treated that is almost unthe other in pp. 200-203 ofa book entitled believable. It is also noteworthy that he The ModernAsphalt Pavement, by Clifdoes not mention the pecul ar concholdal fordRichardson tthen director of the New fracture so character stic ofgilsomteg l/Vhile the real nature of the material with which Day workedcannot, of course, be known, it is worthy of remark that a great varietyof bitumens besides gilsonite occurs in Utah,and that their presence inDays material might account for the low specific gravity of the latter,as well as for some of his results that are absolutely at variance withthe real properties of gilsonite. v I

In a later paper (Am. Philoso hical Society, Proc., wVol. 37, pp.1711?4, 1898), Day tells of making, by distillation of pine sawdust andfresh herring, a substance whichhe found practically indistinguishablefrom native gilsonite.

I have discovered that by suitable treatment,giving rise to phenomenaand results quite different from anything indicated by Day, and itselfalso very different in many respects,-gilsonite can be made the basisfor the production of a great variety of commercially useful products,mostly of y a character and with properties so far from Days account (orfrom any known products, for that matter) as to demonstrate theiressential novelty very clearly. It is possible, I have found, to do thisin such Wise that almost the entire substance .of gilsonite willreappear in the form of useful products. All this will be fullyelucidated by my description hereinafter of the best practical mode ofprocedure for the purposes of my invention at present known -to, me, andof its results.

While physically homogeneous and of relatively simple composition,chemically gilsonite is highly complex. Not only does chemical analysisshow that it contains a number of different elements, but there are manyindications that its characteristic molecule (or molecules) are of veryhigh molecular weight and of corresponding structural complexity.According to my invention, I break up or decompose this complex materialin such a way that there may be obtained and segregated or collectedseparately a number of different products and classes of products. --Ofthese, part have the character of permanent gases or vaporsuncondensable at ordinary temperatures and pressures; part are vaporscondensable as liquid, mainly oil; and part are in the form of solidcoke. The gaseous portion is of such a character as to be at onceserviceable as fuel or as an illuminant; but it is of con siderablecomplexity, and can be made to yield nitrogenous and other usefulproducts without impairment of its combustive utility. The coke is notonly susceptible of direct use as fuel, or of conversion into fuel gas(of somewhat different character from that obtained as above, but has anitrogenous content that can readily be released and Segregated inuseful form (even as a simple incident of gasification of the coke) ifthe I antecedent operation has been appropriately conducted.

7 The liquid products present the utmost variety and complexity, andhave, moreover, a nitrogenous content very readily segregated in usefulform. Though the mixture or aggregate of them resulting from thedecomposition is, indeed, at once directly utilizable, their specificproperties are so diverse that they can generally be utilized to bestadvantage when more or less separated from one another,or, at least,divided up into relatively homogeneous lots or fractions, so to speak.These fractions may be used directly; or-further treated to bring theminto a more useful state; or made the basis or raw material for thepreparation of other valuable products.

In its more complete or integrated form (designed to recover or utiliz'ethe entire substance of gilsonite as fully and advantageously as maybe), my process involves a first main step that is most readily carriedout by progressive distillation of the ilsonite, destructive incharacter, toget ier' with further or subsidiary main steps that may becarried out by combustion of the coke from the initial distillation,-and by redistillation of the primary crude oil distillate (repeated anumber of times in; some cases) in the nature of fractionation orreduction. If it goes far or high enough, redistillation will usuallyinvolve some destructive action, with resultant decomposition ofheavier, higher-boiling, more viscous portions or com onents of oilsubjected thereto, and a yield of lower boiling oils freely liquid atordinary temperatures, and ultimately some coke. Preferably, of course,the vapors from all distillations will be appropriately chilled orotherwise treated: to segregate and recover various different usefulcomponents separately. From the description of my preferred mode ofprocedure, however, it will become apparent that various benefits andadvantages of my invention can be realized even when one or more of theabove-indicated steps is omitted,and even, indeed, when the vapor fromthe initial distillation of gilsonite is not collected or condensed.

It may be noted as a point in the economy of my complete process thatburning of the fuel products obtained as described above (the two lotsor kinds of fuel gas, in particular) affords all the heat necessary forcarrying out its main steps of distillation, so that the process is thusthermally balanced or self-sustaining. Another important point is thatthe unconsumcd portion of certain reagents required or advantageouslyused for treatment of fractionated liquid products can be utilizedcompletely and very advantageously in the and connected to a suitablecondenser,

such as an iron pipe condenser water-cooled. Any convenient quantity ofgilsonite may be charged,-say (300 pounds to several tons. The stillbeing closed and heat applied gradually, I the gilsonite will liquefyandcollect in the bottom of the still, and vapor .and gas evolvingfrom'it will fill the top of the still and pass over into the condenser.

As the heating progresses, temperature readings should be taken fromtime to time on the body of vapor in the upper ortion of the still, aswell as on the body of liquid beneath it. (Excepting as there may bespecial occasion for distinguishing them, I here and hereinaftercomprehend mingled gases and vapors under the single term vapor, forthe, sake of brevity. Otherwise, I have applied these' terms inaccordance with familiar popular usage, having reference to the usualstate of substances at ordinary temperatures. For convenience, I referto various stages of operations by the corresponding temperatures of thevapor then over the undistilled residue, unless otherwise speciallynoted.) The effect of the progressive heating of the gilsonite is togradually break it up and decompose it chemically, as abovementioned,whence, mainly, the evolution of vapor. The coming off ofvapor'from the still begins at a temperature of some 165 F., andcontinues up to or even beyond coking temperatures.

It is a difiicult matter to describe. the process, or to determine inwhat order various products are formed or come Ofi,.

since the coming oil of particular products depends on the stabilityunder heat of the highly complex chemical combinations amongst theconstituents of gilsonite, as well as upon the boiling points of theproducts themselves. The matter is further complicated, no doubt, by theliberation, formation, and decomposition of intermediate products,both'in the body of liquid: and

in the body of vapor. 1 Speaking generally, however, and-with referenceto the bulk or predominant amounts of the several products, thefollowing may be said:

' In the earlier stages of the distillation, mainly oil and water vaporscome'ofl; and in the later stages, oil vapor with proportionatelyincreased amounts of unconden sable gas. Near the end of thedistillation, sometime after the bulk of the water,a minor butsubstantial amount of heavy oil vapor comes off that is condensable atrela tively high temperatures, and isthick and gummy at ordinarytemperatures (readily attainable by water cooling) appropriate forcondensing the bulk of the total amount of oil vapor. The maximumdestructive effect and evolution of gas occur just before condition ofcoke,the actual amount of gas being quite substantial at this stage aswell as previously. Both at'this stage and as a whole, the distillationgas has a greater proportionate nitrogenous content thanv that from anyother hydrocarbonaceous material.

Up to the point where the'vapor temperaand after the undistilled residuereaches the ture approaches some 550 -F., the distilla--- tion may becarried out as rapidly as the.

contents of the still can be made to absorb heat. At this point,however, some exothermic or other peculiar a tion occurs, so that theevolutionof vapor in the still tends to become excessively rapid.Unless, therefore, the previous heat ng has been especially slow, it isnecessary to reduce the application of heat very greatly as thiscritical point is approached, in order that the then undistilled liquidresidue may not spew out of the'still and even be carried over into thecondenser, and clog it up so as. to render it unusable. In practice, itwill usually be found convenient to cut down the fire some 100 F. inadvance of this temperature. Once thiscritical point is well passed, thefire may be increased and the distillation pushed on as rapidly asdesired to its conclusion.

\Vhile the vapor coming off from the still may all be led into the ironpipe condenser, as above suggested, and all of the strictly vaporousportion thereof there condensed and collected as a liquid, a slightlydifferent procedure is preferable. At the temperatures in the condenserappropriate for condensing other portions, the above-mentioned heavierportion of the oil vapor is of such thick, gummy consistency that itwould tend to clog up the condenser very annoyingly. In order that thisminor, heavy portion of the normally liquid-products may be condensedand collected separately,-without entering the main condenser at all-thevapor fromthe still ma first be chilled preliminarily, so to spea I, tocondense and separate out this heavier, high-boiling portion, and thenfurth r chilled in the condenser to condense otier portions. 'VVhile Iand added to the liquid products from the condenser itself. Therelatively high temperature of the pipe appropriate for caus ingseparate condensation of the heavy portion of the vapor asabovedescribed (and naturally existing between still and trap) avoids anytroublesome intermingling of the thick, gummy oil condensate while stillvery hot with accumulations of condensed water' vapor from thedistillation (which latter, as already stated, precedes the heavy oilvapor), since such water vapor naturally passes on through the hot pipeuncondensed. In cases Where the trap cannot be located close enough tothe still to obviate all risk of substantial collection of water andcorrespondingly low-boiling oil therein, it is advisable to draw offsuch accumulation from time to time before the troublesome heavy oilcomes over, so as to avoid intermingling of the very hot heavy oilcondensate with the water and the consequent sudden and dangerousevolution of steam,- which might at the least cause spewing of water andheavy oil out of the trap into the condenser or back into the still.

Besides taking care of the troublesome heavy oil vapor, the trap affordsa measure of protection against the possibility of similar troubles fromspewing over of the still into the condenser because of too rapidheating at the critical temperature above mentioned. Such a possibility,of course, is an additional reason for avoiding accumulation of water inthe trap.

The truly gaseous portion of' the distillation products will passuncondensed through the condenser and be collected separately. Thenitrogenous portion of this gas can be segregated and secured in theform of aqueous ammonia or of ammonium sulphate, by subjecting the gasto an aqueous or sulphuric acid scrubbing operation. The sul phuricreagent ordinarily to be preferred for such purposes is sulphuric acid,rather than sulphuric anhydride.

The gas thus scrubbed contains a relatively small amount of lighthydrocarbon oil (not condensable by the temperatures generally attainedin the ordinary water-cooling described above, and hence unrecoverablethereby) suspended or otherwise present therein: this may be allowed toremain in order to enhance the luminosity of the gas. It may, on theother hand, be separated out and secured by a scrubbing operation with alight oil (such as spindle oil) and subsequent distillation of this oil.If this oilscrubbing is resorted to, it should preferably be done priorto the water or sulphuric scrubbing.

The final point to which the distillation is carried may vary somewhat,according to the products most desired, and the use or disposition to besubsequently made of them,

hand, the maximum temperature of the coke in the still should beregulated with reference thereto, and kept within the limit of .nitrogenfixation, which for nitrogen extraction or recovery in such useful formas ammonia by combustion gasification. of the coke is about thetemperature of initial combustion or kindling of the latter, around 1000F. Again, it is desirable that the final or maximum temperature besufficient to yield coke that is dry and stable at such temperature, andalso unmeltin at the temperatures attained in incompl ete combustion ina gas-producer, so that it may be gasified andits nitrogen recovered inthat manner. Final temperatures ranging between some 850 F. and 1000 F.meet both these conditions, and even somewhat higher temperatures yieldcoke retaining a major proportion of the original nitrogen of thegilsonite unfixed and releasable for recovery. Final temperatures towardthe lower limit of the range retain'in the dry, solid coke the maximumproportion of nitrogen,the maximum consistant with non-melting dryness,at any rate. While a temperature of 850 F., for the solid coke productof the distillation need not in ractice be exceeded, I generally prefera nal temperature of about 900 F., as giving the best over allefliciency.

Taking representative percentages, the products into which the gilsoniteis converted 10y the initial distillation are about as folows:

Light hydrocarbon, 2; ammonia (NH free, .25; hydrocarbon fuel gas,12.75; distillate, 55; coke, 30.

In the absence'of the oil-scrubbing operation, the hydrocarbon fuel gasfrom the primary distillation is a mixture with an average heating valueof as high as 930 B. t. u. per cubic foot. It contains methane and otherhydrocarbons, so that it can be burned with a luminous flame or used toenrich and render luminous other fuel gas. Because of its hydrocarboncontent, it may conveniently be distinguished as hydrocarbon fuel gas,Its average percentage composition is about as follows:

G0,, 2.8; illuminant hydrocarbon, 6.6; O, .4; G0,, 5.8; 0H,, 77.6; H,4.5; N, 2.3.

The hydrocarbon oil distillate extracted from the gas by theoil-scrubbing operation is a very light, colorless, volatile liquid,vaporizingrapidly at ordinary temperature, and boiling from F. to 200 F.It is removed at the conclusion of the distillation,

after it has cooled sufliciently. Unless the coke has been superheatedbeyond the favorable-range indicated above, its unfixed nitrogen contentis quite substantial, exceeding 1%, and, in fact, amounting to some 5 or6%,i. e substantially some 80% of the total nitrogen content of theoriginal gilsonite,whi'ch is an unprecedently high nitrogen content andproportion of retention for a distillation coke from hydrocarbonaceousmaterial. This nitrogenous coke may be gasified by incomplete combustionin a byproduct gas-producer, and the nitrogenous portion of theresultant gas separated from the remainder and recovered (by means of awater or a sulphuric acid scrubbing operation) in the form of aqueousammonia or of ammonium sulphate. As the ash content of the coke amountsto but a trifling 2 to 4%, it is desirable to mix a substantialproportion of foreign ash or other inert refractory material with thisunprecedently rich coke as it is fed into the producer, to guard againstmelting out of the gratesor other injury from excessive temperatures.

The significance of the above-mentioned upper temperature limit of 1000F. for the coke during distillation and its coincidence with the initialcombustion or kindling temperature of the latter may now be'readilyunderstood, by considering that in order to release nitrogenous productsin the gas producer, it is naturally necessary to surpass the limit ofthe distillation,-during which the nitrogen amenable to all temperaturesthen attained was driven off in the distillation vapor. Such nitrogen asfails to come off at the lower temperatures attained in gas producercombustion continues its fixation under the higher temperatures theresubsequently attained,. and eventually comes off only in forms (otherthan ammonia) in which it is not usefully recoverable. It will also beseen that the lower the final or maximum temperature of the coke in thedistillation the greater its possible nitrogen content,which for thelimit of distillation temperature above indicated will be unfixed andreleasable for re covery as ammonia.

It will be apparent, therefore, that my technique of controlling thedistillation with reference to releasability of nitrogen from the cokeinvolves a sharp departure from ordinary practice in the treatment ofhydrocarbonaceous materials, according to which distillation is pushedto the utmost limit with a view to getting out as much ammonia and oil,etc., as possible in the distillation vapors, and the coke left to takecare of itself.

The remainder of the gas from the coke, after the' scrubbing operationfor extraction of ammonia, is a mixture of carbon monoxide, carbondioxide, hydrogen, nitrogen, etc., suitable for use as fuel gas, andconveniently distinguishable as carbonaceous fuel gas. It has a fuelvalue of about 140 B. t. u. er cubic foot, and is practicallynon-luminous. A portion of this secondary fuel gas may be satisfactorilyI enriched and rendered luminous by mixture therewith of the primaryhydrocarbon fuel gas. The average ercentage composition of thissecondary uel gas is about as follows:

CO 15; CO, 11; CH,, 3.5; H,-24; N, 46; illuminant hydrocarbon, .5. Y

Practically all of the coke is used up in the gas-producertreatment,-the ash amounting to but a trifling 24%, as already noted.

The total liquid distillate (i. e., the mixture of the portions drawnoff from the condenser and the trap) contains some 2 to 5% of water, andin this water is dissolved the nitrogenous content of the crudedistillate above referred to, in the form of ammonia. This water mayeasily be eliminated and the aqueous ammonia segregated and secured byallowing the water to settle out in a settling tank. If desired, it maybe converted into ammonium sulphate by means of sulphuric acid treatmentsuch as indicated above. in connection with the scrubbing of the primarydistillation gas. As it comes from the settling tank, the primary crudedistillate is a reddish brown oil with a een fluorescence, decidedlyliquid at or inary atmospheric temperatures, and having. a specificgravity of about .875 at 60. F. After standing a While it loses itsfluorescence, and 1 becomes dark brown to black, and absolutely opaquein sections of any considerable thickness. It has a characteristicpungent odor, difiicult to define, and rather unpleasant. It begins toboil at about 140 F., and distills completely below 700 F; it flashes inthe air at ordinary temperatures. It contains a very high percentage ofunsaturated hydrocarbons,usually about 60%,aswell as combined nitrogenin proportions (some 0.2%) that are likewise unprecendently high ascompared with other mineral oils. It also contains a relatively highproportion of the wax hereinafter mentioned, amounting to some 1%. a inwater, but completely soluble in benzole and carbonbisulphide, andmiscible in all proportions with petroleum and petroleum products,turpentine, and pine oil. It presents a remarkable combination ofparaflinic characteristics (in respect of cold oil distillate is ahighly complex material,

capable of fractionation to an almost unlimited extent. The differentproducts thus obtainable from it not only exhibit diverse propertieswhich fit 'them for a great variety of industrial uses, but aresuscepible of chemical treatment, purification, modification, andconversion to yield a great variety of new and useful substances andmaterials. In practice, it is most advantageous to initially separatethe crude oil into a comparatively small number of fractions, by dryredistillation in a suitable heated iron or steel still. Theredistillates may, if desired, be further purified by treatment withsulphuric acid and subsequent neutralization of the excess of reagentwith alkali, such as caustic soda in aqueous solution. The followingexamples (wherein the temperatures given are the vapor temperatures inthe still, unless otherwise stated) will sufliciently illustrate themost convienent methods of redistillation:

(1) Condense separately the vapors coming from the still up to 475 F.and from 475 F. to 600 F.,-subsequently drawing of? as residuum the oilunvaporized at the latter temperature, or allowing it to remain and mixwith the next charge of crude oil.

(2) Condense separately the vapors up to 475 F.; from 475 to 650 F.; andfrom 650 F. until the temperature of the material in the bottom of thestill is about 850 F. By this procedure, an amount of coke equal toabout 2% of the crude oil charge will be produced; it may be treated inthe gasproducer along with that from the primary distillation. Thepercentages of the products thus obtained are about as follows:

Light oil, 24; medium oil, 35; heavy oil 36; coke 2.5; gas, and water,etc., 3.5.

In either of these cases, considerable de structive action occurs in theproduction of the higher fraetion, especially the last.

(3) Three fractions nearly similar to those described under (2) may beobtained at temperatures some 100 1 lower than those mentioned bycarrying out the redistillation as described in U. S. Patent 877,620,granted Jan. 28, 1908, to W'ells, blowing carbon dioxide or otherinsertpermanent gas through the liquid in the still. In this case, thedestructive action is much less. It is advantageous to pass the gas andvapor coming off through a filter of fullers earth in the dome of thestill, on its way to the condenser. A residuum f heavy oil willpreferably be left in the still, as described under The light distillateproduced in any of these ways is a vellow oil which becomes red onstanding. fter sulphuric purification, it may be desirable to redistillit in order to improve its colorleaving as residuum, in the still thesmall portion of the oil not coming off below 425 F. The resultantreduced and purified product is a light, colorless, completely volatileoil; with mild terpene odor slightly suggesting turpentine; of specificgravity about .74 to .78; and of exceptionally high and diverse solventcapacity for substances used in the paint and varnish industry:specifically, its solvent capacity for varnish gums is substantiallygreater than that of the most similar petroleum derivatives. Its terpenecharacteristic is considerably more marked than in the case of refinedpetroleum, especially after prolonged standing.

The intermediate distillate oil is a yellow oil with green fluorescencewhen fresh; on

standing it becomes first red and then,

eventually, a deep reddish brown. Its specific gravity is about .870. Itis capable of use as gas oil or fuel oil without sulphuric acidpurification. It is more reactive to sulphonating reagents than the mostsimilar mineral oil distillates from petroleum or other knownhydrocarbonaceous materials. It is susceptible of sulphonation treatmentwith oil of vitriol and oleum (preferably after the preliminarysulphuric purification with a small percentage of oil of vitriol) toyield various useful roducts. These include a residual which a terneutralization and redistillation is a thin, clear oil, substantiallycolorless, odorless, and tasteless; a sulphonation reaction oil ofhighly useful semi-drying properties; and a water-soluble product withthe useful properties (hydrolizing, detergent, emulsifying) generallycharacteristic of true sulphonic substances. These last two products canbe segregated by diluting the sulphonation sludge with an equal amountof water and allowing the solution to stand at a temperature of 150 F.and separate into layers by gravity. Of the resultant layers, the topcomprises the reaction .oil and the middle the aforesaid water-solublesulphonic product, while the bottom comprises most of the unconsumedacid diluted with water. The separation is a matter of differentspecific gravities and preferential solubilities. For example, ata'concentration of about 30 Baum (corresponding to a specific gravity of1.2609 at 60 F. for the diluted sulphuric acid, the water-soluble sul- 7phuric product will be practically insoluble able sulphuric acid. Thespecific gravity .of

' F., as compared with 120 F. for an illustrative ordinary p'arafline.The pressed the sulphuric product is very close to 1.000,

and that of the reaction oil is lem than 1.000: hence the separationinto layers as described.

The middle layer may be freed from contaminatingorganic impurity byneutralization, which sets the impurity free to rise to the surface andbe removed,-or, in like F b manner, by free dilutionwith water.

The heavy distillate oil is a somewhat viscous reddish-yellow oil withgreen fluorescence when freshly prepared; onstanding it becomes almostblack,-or brown in a thin film. Its specific-gravity is about .927. Bothit and the residual oil redistillate .(if produced) are suitable for useas flotation reagent without further treatment. The residual oil has aspecific gravity of about .933.

Generally speaking, gilsonite oil fractions or redistillates(includingthe three typical ones just described) have the samestrikingly high content of combined nitrogen and of unsaturatedhydrocarbons as the crude primary distillate described above, and thehigher boiling fractions contain the gilsonitic wax referred to. Thepeculiar combination of paraflinic and asphaltic properties is even moremarked in the high boiling fractions than in the crude distillateitself.

-The heavy distillate is suitable for the manufacture of lubricatingoil. For this purpose, it may be purified by treatment with 3 to 10% ofoil of vitriol; neutralized with caustic soda or other alkali; washedwith water; and then chilled to about 32 F. and filter-pressed. Thispressing removes from the oil a material which, after re-pressing andfiltering through fullers earth, be-

comes a merchantablewazqhard and crystal line, darkyellow to reddish incolor, with 1 a melting point of about 135 F. to 170 oil is thenfractionated or reduced according to the particular variety of lubricantdesired. The resultant refined products are viscous, yellowish red oils,with @pronounced green fluorescence; they have specific gravities of 0.9and upward; they give, a flash test of not less than about 350 F.; theyboil at temperatures exceeding 450 F., and, for

the most part, above 600 F. They are stable against decomposition intoproducts unsuited to lubrication under even the unfavorable conditions-of internal combustion engine cylinder lubrication; and they are inertwith respect to ordinary metals, so that they will not injure machineparts.

The anomalous character of gilsonitic oils already referred to isstrikingly ap Califor 1 g nia Paraflinic asphaltic i (2) -Grav1ty Baume.1 24. 8 24.3 31 25. 9

Specific-gravity .9044 .9073 8. 06 .8980

his te 370 305 400 370 Viscosity at 100 F. 212 319 160 173 Viscosity at212 F 47 46 40 42 Cold test 35 0 24 33 .Thus it will be observed thatfor similar gravities the asphaltic and gilsonitic lubricating oils haveflash points below those for even lighter parafiinic oils; while thegilsonitic oil has viscosities which, if not asphaltic, are intermediatebetween those of .paraflinic and asphaltic oils. The cold test of thegilsonitic' lubricating oil and the wax obtained in its production asdescribed above indicate its paraflinic character.

The unconsumed portion of thesulphuric acid used in the variouspurifying and sulphonation treatments above described can be used as areagent for the segregation of nitrogenous products from the primarygas, liquid, and coke products'as above set forth. Sulphonation of theintermediate distillate described above will afford enough uchunconsumed acid for this purpose.

Having thus described my invention, I claim:

1. A gilsonitic oil; of specific gravity about .875 at 60 F.;reddish-brown with green fluorescence when fresh, but losing suchfluorescence and turning reddish brown to black after standing; boilingfrom 140 F. to 700 F. and flashing in air at ordinary temperatures; ofunpleasant pungent odor; containin -high ,meltin wax and unsaturated hyrocarbons in liigh proportion as com ared with petroleum; .and yieldingby ractionation a light fraction with terpene odor, and a heavy fractionitself yielding lubricating oils of paraflinic character having therelations of flash to specific gravity generally characteristic ofasphaltivlubricating oils.

2. A gilsonitic oil when fresh, reddish brown with green fluorescence,and turning and heavier lubricating oil with paratlinic cold testcharacteristics and asphaltic relations of flash to specific gravity.

3. A gilsonitic oil of specific gravity about .875 at 60 F.; boilingfrom 140 F. to 700 F., and flashing in air at ordinary temperatures; ofunpleasant pungent odor; containing high meltingwax, and also nitrogenand unsaturated hydrocarbons in high proportions as compared withpetroleum; and yielding, by fractionation and refinement, light oil withterpene odor more marked than.

that of refined petroleum.

4. A gilsonitic oil containing hard, high melting crystalline wax; andyielding, by

fractionation and refinement with sulphuric acid lubricating oil ofparaflinic character with asphaltic relations of flash to specificgravity. 1

5. A gilsonitic oil of pungent odor; containing nitrogen and unsaturatedhydrocarbons in high proportions as compared with petroleum; andyielding, by redistillation and refinement with sul huric acid, oil withterpene odor more mar ed than that of refined petroleum.

In testimony whereof, I have hereunto signed my name at Maurer N. J this16th day of Sept. 1922.. Y v

' CHARLES N. FORREST.

